CN104372394A - Preparation method for oxide ceramic layer - Google Patents
Preparation method for oxide ceramic layer Download PDFInfo
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- CN104372394A CN104372394A CN201410316971.7A CN201410316971A CN104372394A CN 104372394 A CN104372394 A CN 104372394A CN 201410316971 A CN201410316971 A CN 201410316971A CN 104372394 A CN104372394 A CN 104372394A
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Abstract
The invention belongs to the field of material engineering, and concretely relates to a preparation method for an oxide ceramic layer. The preparation method comprises the following steps: (1) pre-preparing an insulating barrier layer on the surface of an alloy sample by using a plasma electrolysis oxidation process or a rare earth salt chemical conversion process; (2) preparing a nitrate aqueous solution with a certain concentration; and (3) putting the alloy sample obtained in the step (1) in the solution obtained in the step (2), putting the alloy sample at the cathode while the anode is stainless steel or a graphite electrode, applying high-energy pulse voltage on the alloy sample, and performing deposition for 0.5-3 h on the alloy surface, so as to prepare the ceramic layer on the surface of the alloy sample. The electrolyte for plasma electrolysis oxidation, chemical conversion and cathode plasma electrolysis deposition does not contain toxic cations harmful to human body and environment, the solution is simple in compositions and easy to control, and the technology is stable. By employing the cathode plasma electrolysis deposition method for pre-preparing a barrier membrane, and the technology is simple and easy to operate, and is suitable for industrialized production.
Description
Technical field
The invention belongs to material engineering field, be specifically related to a kind of preparation method of oxide ceramic layer.
Background technology
The preparation method of oxide ceramic layer has multiple.At present, the method for comparative maturity has plasma spraying, and vapour deposition in recent years also reaches its maturity.Plasma spraying is loose to the requirement of coated material, and deposition is high, easy and simple to handle.But the laminate structure of coating and hole etc. all may become the formation of crack causing coating failure, cause properties of coating to be restricted.
Vapour deposition gained ceramic layer over-all properties is better, but its sedimentation rate is lower, equipment manufacturing cost is expensive, manufacturing cost is high, affect by element vapour pressure, the Composition Control of coating is more difficult, and matrix part needs heating, specimen size can not be too large, thus limit the industrialization promotion of this method to a great extent.Although the methods such as application hard anodizing, ion plating, chemistry or physical vapor deposition can prepare oxide ceramic layer on light alloy surface, this ceramic layer can improve the surface property of matrix to a certain extent, but still is apparent not enough when the service condition under high speed and high contact stress; The treatment technology simultaneously had also can bring certain environmental problem.In addition, the oxide ceramic layer major part adopting the methods such as laser remolten, chemical vapour deposition, magnetron sputtering to prepare also only rests on the laboratory study stage, does not form the utilisation technology of large-scale promotion.
Plasma electrolytic oxidation technology (Plasma Electrolytic Oxidation, be abbreviated as PEO) be development in recent years a kind of light alloy surface ceramic deposition treatment technology rapidly, cause the great attention of science and industrial community both at home and abroad, and owing to being called as the cleaning procedure of non-ferrous metal surface modification to the innocuousness of environment and human body.It is a kind of novel process at light alloy surface in situ grow oxide ceramic film, there are higher hardness, wear resistance, solidity to corrosion and bonding strength etc., but this technology can only be applied to the valve metal surfaces such as Al, Mg, Ti to a great extent, the ceramic layer principal crystalline phase formed is the oxide compound of matrix metal, is difficult to according to requirements adjust ceramic layer composition.
Different from PEO technology, developed cathode plasma electrolytic deposition technology (CathodicPlasma Electrolytic Deposition in recent years, be abbreviated as CPED), it combines cathodic electrochemical deposition method (Cathodic Electrochemical Deposition, be abbreviated as CELD) and the advantage of PEO technology, using metallic matrix as negative electrode, supporting electrode is as anode, high energy pulse voltage is applied while cathode electrodeposition, make to be deposited on cathode surface in advance there is the sull generation puncture of insulation of high electrical resistance and produce micro-arc discharge, utilize the high-energy of the differential of the arc that the oxyhydroxide of cathodic electrochemical deposition is converted to the oxide compound of crystalline state, and finally under the high temperature of micro-arc discharge generation, sinter formation ceramic coating.Ceramic layer is formed at deposition process situ, and forms metallurgical binding between matrix, has good bonding force.Which overcome usual CELD method and need aftertreatment---to the shortcoming that coating sinters, and in order to avoid coating shrinkage, cracking and make coat-thickness limited in sintering process.The two advantage of CPED combine with technique, to matrix metal without particular requirement, the oxide compound kind of deposition is many, cathode filming efficiency is improved by cathode plasma electric discharge, and the electric discharge of the deposition of coating, cathode plasma and sintering almost complete in solution simultaneously, so be not subject to the various oxide ceramic layers of matrix metal restriction in metallic surface preparation by the method.
In recent years, He Yedong, Yang Xiaozhan etc. utilized CPED technology to prepare ZrO at Fe25Cr5Al alloy surface
2-Y
2o
3ceramic layer, the prefabricated needs of barrier film flood 30 ~ 40 times in metal salt solution.The method applies for national inventing patent, and the patent No. is ZL01118541.4, and foolish brave, Li Xinmei etc. have studied electrical parameter and electrolytic solution composition (Al (NO
3)
3, ethanolic soln, deionized water) impact on Ti cathode plasma electrolysis deposition aluminum oxide coating layer, but less to the performance analysis of coating.The people such as Xue Wenbin are at 0.4mol/l Al (NO
3)
39H
2utilize cathode micro arc deposition technique in O and ethanolic soln, successfully prepare aluminum oxide coating layer on titanium surface, research shows coating and basal body binding force better, has higher resistance to high temperature oxidation and corrosion resistance.The people such as Han Wei, He Yedong are discharged by cathode surface generation air film in aqueous the energy of the plasma body produced, and the settling direct sintering that the ion in the aqueous solution is formed at the cathode surface of Fe25Cr5Al alloy becomes ZrO
2-Y
2o
3ceramic coating.The people such as Li Xijin utilize cathode micro arc discharge sedimentation method, with Al (NO
3)
3ethanolic soln is electrolytic solution, has prepared one deck continuous print Al on TiAl alloy surface
2o
3film, result shows: rete has valuable help to improving TiAl alloy high temperature oxidation resistance.
Present Research both domestic and external shows, the domestic and international research object for this technology mainly concentrates on steel and titanium alloy at present, very few to the research of Al alloys andMg alloys; Also have that bath composition is single, barrier film precasting process is difficult to the limitation such as guarantee.
Summary of the invention
Goal of the invention: for solving the problems of the technologies described above, the invention provides a kind of preparation method of oxide ceramic layer.
Technical scheme: a kind of preparation method of oxide ceramic layer, comprises the steps:
(1) by plasma electrolytic oxidation method or rare-earth salts chemical transformation at the prefabricated insulation barrier in alloy sample surface;
(2) configuration concentration is 5 ~ 50g/L nitrate aqueous solution;
(3) alloy sample described in step (1) is placed in solution described in step (2), described alloy sample is placed in negative electrode, anode is stainless steel or Graphite Electrodes, high energy pulse voltage is applied to described alloy sample, at described alloy surface deposition 0.5 ~ 3h, then prepare ceramic layer on described alloy sample surface.
A kind of preferred version as a kind of in the present invention preparation method of oxide ceramic layer: described in step (1), alloy sample is before prefabricated insulation barrier, also needs pre-treatment, comprises the following steps:
(11) by described alloy sample acetone or alcohol washes;
(12) described for step (11) alloy sample sand paper is polished;
(13) by described for step (12) alloy sample washed with de-ionized water.
A kind of preferred version as a kind of in the present invention preparation method of oxide ceramic layer: after ceramic layer is prepared on the described alloy sample surface of step (3), also needs to rinse with deionized water.
A kind of preferred version as a kind of in the present invention preparation method of oxide ceramic layer: the method for the prefabricated insulation barrier of using plasma electrolytic oxidation in step (1), comprises the following steps:
(11) according to silicate 1 ~ 30g/L, phosphoric acid salt 1 ~ 20g/L, pH adjusting agent 1 ~ 5g/L prepare electrolytic solution, and solvent is deionized water;
(12) electrolytic solution described in step (11) is imported as in the stainless steel tank of negative electrode, described alloy sample, as anode, adopts the direct current pulse power source way of output to carry out the prefabricated insulation barrier of plasma electrolytic oxidation process to described alloy sample.
A kind of preferred version as a kind of in the present invention preparation method of oxide ceramic layer: above-mentioned silicate is water glass or potassium silicate; Above-mentioned phosphoric acid salt is sodium phosphate or potassiumphosphate, and above-mentioned PH conditioning agent is potassium hydroxide or sodium hydroxide.
A kind of preferred version as a kind of in the present invention preparation method of oxide ceramic layer: the condition of carrying out plasma electrolytic oxidation process in above-mentioned steps (12) is: electric current 3 ~ 10A/dm
2, frequency 100 ~ 300Hz, dutycycle 30 ~ 50%, oxidization time is 3 ~ 10min.
A kind of preferred version as a kind of in the present invention preparation method of oxide ceramic layer: the method adopting the prefabricated insulation barrier of the chemical transformation of rare-earth salts described in step (1), comprises the steps:
(11) according to cerous nitrate or Cerium II Chloride 1 ~ 50g/L, hydrogen peroxide 0.1 ~ 10ml/L adds deionized water to 1L, regulates PH to 4 ~ 6;
(12) rare earths salt described in step (11) is warming up to 50 ~ 90 DEG C, described alloy sample is put into described rare earths salt reaction 20 ~ 60min.
A kind of preferred version as a kind of in the present invention preparation method of oxide ceramic layer: nitrate described in step (2) is one or more in zirconium nitrate, aluminum nitrate, magnesium nitrate, Titanium Nitrate, Yttrium trinitrate, nickelous nitrate, nitrocalcite, cupric nitrate, chromium nitrate, iron nitrate or cerous nitrate.
A kind of preferred version as a kind of in the present invention preparation method of oxide ceramic layer: the condition of carrying out high energy pulse in step (3) is for being pulsed current 3 ~ 30A/dm
2, pulsed voltage 300 ~ 1000V, frequency 100 ~ 1500Hz, dutycycle 5 ~ 50%.
A kind of preferred version as a kind of in the present invention preparation method of oxide ceramic layer: described alloy refers to the one in magnesium alloy or aluminium alloy or magnalium.
Beneficial effect: 1, plasma electrolysis oxidation of the present invention, chemical conversion and cathode plasma electrolytic deposition electrolytic solution is not containing the toxic positively charged ion to human body and bad environmental, and solution composition is simple, is easy to control, not containing easily decomposing composition, process stabilizing.
2, adopt the prefabricated barrier film technique of cathode plasma method for electrodeposition of the present invention simple, easy handling, and without the need to follow-up sintering process, simple to operate, be suitable for suitability for industrialized production.
3, namely the present invention has the excellent bonding strength of plasma electrolytic oxidation growth in situ oxide ceramic layer, there is again cathode electrodeposition not by advantages such as matrix metal restrictions, the oxide ceramic layer of various premium properties can be prepared on non-ferrous metal and ferrous metal.
4, the ceramic layer prepared by the present invention is not by the restriction of matrix metal, can can dissolve various metal-salt in proportion in the solution easily according to the difference of metal-salt kind in electrolytic solution and obtain single oxide ceramic layer or the multinary oxide coating layer of distributed components, the oxide compound kind deposited is a lot, as long as the oxyhydroxide in electrolytic solution corresponding to metal ion is indissoluble thing, then can deposit the metal oxide of any kind within the scope of this.Can according to salts solutions such as the nitrate of the non-ferrous metal such as the different choice Al of deposition oxide, Mg, Ti, Cu, Zr, Y, Ce, Ni, Ca and muriates, also can select the salts solution such as nitrate and muriate of the ferrous metal such as Fe, Cr, thus various oxide ceramic layer can be deposited according to demand.
Accompanying drawing explanation
Fig. 1 is the cathode plasma electrolytic deposition ZrO of the prefabricated insulating barrier films of plasma electrolytic oxidation method using process of the present invention
2the SEM shape appearance figure of surface ceramii layer
Fig. 2 is cathode plasma electrolytic deposition ZrO
2the XRD figure spectrum of ceramic layer phase composite
Fig. 3 is the cathode plasma electrolytic deposition Al of the prefabricated insulating barrier films of plasma electrolytic oxidation method using process of the present invention
2o
3the SEM shape appearance figure of surface ceramii layer
Fig. 4 is cathode plasma electrolytic deposition Al
2o
3the SEM shape appearance figure in ceramic layer cross section
Fig. 5 is the cathode plasma electrolytic deposition ZrO of the prefabricated insulating barrier films of plasma electrolytic oxidation method using process of the present invention
2-Y
2o
3the SEM shape appearance figure on composite ceramic layer surface
Fig. 6 is for being cathode plasma electrolytic deposition ZrO
2-Y
2o
3the SEM shape appearance figure of composite ceramics layer cross section
Fig. 7 is cathode plasma electrolytic deposition ZrO
2-Y
2o
3the EDS EDS maps of composite ceramics layer cross section
Fig. 8 is the deposition ZrO of the insulating barrier films using the rare-earth salts chemical transformation of process of the present invention to prepare
2-Y
2o
3the SEM shape appearance figure on composite ceramic layer surface
Fig. 9 is the cathode plasma electrolytic deposition ZrO of the prefabricated barrier film of rare-earth salts chemical conversion process using process of the present invention
2-Y
2o
3the SEM shape appearance figure of composite ceramics layer cross section
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.
Specific embodiment 1
By aluminum alloy sample with first cleaning with acetone; Use sand papering again, finally clean, stand-by with deionized water rinsing.Then point the following steps complete preparation:
The first step: by plasma electrolytic oxidation method at the prefabricated insulation barrier in aluminum alloy sample surface:
First according to water glass 1g/L, sodium phosphate 20g/L, sodium hydroxide 1g/L prepare electrolytic solution, and solvent is deionized water; Import above-mentioned electrolytic solution as in the stainless steel tank of negative electrode, aluminum alloy sample, as anode, adopts the direct current pulse power source way of output to carry out the prefabricated insulation barrier of plasma electrolytic oxidation process to aluminum alloy sample again.The condition of carrying out plasma electrolytic oxidation process is: electric current 3A/dm
2, frequency 100Hz, dutycycle 30%, oxidization time is 3min.
Second step: configuration concentration is the 5g/L zirconium nitrate aqueous solution;
3rd step: the zirconium nitrate aqueous solution aluminum alloy sample in the first step being placed in second step; Aluminum alloy sample is placed in negative electrode, and anode is stainless steel, applies high energy pulse voltage to aluminum alloy sample, at alloy surface deposition 0.5h, then prepares ceramic layer on aluminum alloy sample surface.The condition of carrying out high energy pulse in the 3rd step is: pulsed current 3A/dm
2, pulsed voltage 300V, frequency 100Hz, dutycycle 5%.
Finally rinse with the aluminium alloy of deionized water effects on surface formation ceramic layer.
Fig. 1, Fig. 2 are cathode plasma electrolytic deposition ZrO
2the surperficial SEM shape appearance figure of ceramic layer and XRD figure spectrum.As seen from the figure, surface ceramii layer is formed by the cellular structure of electrochemical deposition substantially, plasma discharge micropore comparatively small amt, and from XRD figure spectrum, ceramic layer all crystallization is complete, by the ZrO of different crystal forms
2composition, so adopt this technique ceramic layer crystallization just can be made complete without the need to follow-up sintering process.
Specific embodiment 2
By magnesium alloy sample with first using alcohol washes; Use sand papering again, finally clean, stand-by with deionized water rinsing.Then point the following steps complete preparation:
The first step: by plasma electrolytic oxidation method at the prefabricated insulation barrier of magnesium alloy sample surfaces:
First according to potassium silicate 30g/L, potassiumphosphate 1g/L, potassium hydroxide 5g/L prepare electrolytic solution, and solvent is deionized water; Import above-mentioned electrolytic solution as in the stainless steel tank of negative electrode, magnesium alloy sample, as anode, adopts the direct current pulse power source way of output to carry out the prefabricated insulation barrier of plasma electrolytic oxidation process to magnesium alloy sample again.The condition of carrying out plasma electrolytic oxidation process is: electric current 10A/dm
2, frequency 300Hz, dutycycle 50%, oxidization time is 10min.
Second step: configuration concentration is 50g/L aluminum nitrate aqueous solution;
3rd step: the aluminum nitrate aqueous solution magnesium alloy sample in the first step being placed in second step; Magnesium alloy sample is placed in negative electrode, and anode is Graphite Electrodes, applies high energy pulse voltage to magnesium alloy sample, at alloy surface deposition 3h, then prepares ceramic layer at magnesium alloy sample surfaces.The condition of carrying out high energy pulse in the 3rd step is: pulsed current 30A/dm
2, pulsed voltage 1000V, frequency 1500Hz, dutycycle 50%.
Finally rinse with the magnesium alloy of deionized water effects on surface formation ceramic layer.
Fig. 3, Fig. 4 are cathode plasma electrolytic deposition Al
2o
3the SEM shape appearance figure in surface ceramii layer and cross section.As seen from the figure, surface ceramii layer is typical cellular structure, and from Cross Section Morphology, ceramic layer top layer is the cellular structure of electrochemical deposition, and be typical CPED ceramic layer tissue topography, internal layer is PEO blocking layer.
Specific embodiment 3
By magnalium sample with first using alcohol washes; Use sand papering again, finally clean, stand-by with deionized water rinsing.Then point the following steps complete preparation:
The first step: by plasma electrolytic oxidation method at the prefabricated insulation barrier of magnalium sample surfaces:
First according to potassium silicate 15g/L, potassiumphosphate 10g/L, potassium hydroxide 3g/L prepare electrolytic solution, and solvent is deionized water; Import above-mentioned electrolytic solution as in the stainless steel tank of negative electrode, magnalium sample, as anode, adopts the direct current pulse power source way of output to carry out the prefabricated insulation barrier of plasma electrolytic oxidation process to magnalium sample again.The condition of carrying out plasma electrolytic oxidation process is: electric current 5A/dm
2, frequency 200Hz, dutycycle 40%, oxidization time is 8min.
Second step: configuration concentration is 10g/L zirconium nitrate and 10g/L yttrium nitrate aqueous solution;
3rd step: the zirconium nitrate and the yttrium nitrate aqueous solution that the magnalium sample in the first step are placed in second step; Magnalium sample is placed in negative electrode, and anode is stainless steel, applies high energy pulse voltage to magnalium sample, at alloy surface deposition 1.5h, then prepares ceramic layer at magnalium sample surfaces.The condition of carrying out high energy pulse in the 3rd step is: pulsed current 20A/dm
2, pulsed voltage 600V, frequency 1000Hz, dutycycle 40%.
Finally rinse with the magnalium of deionized water effects on surface formation ceramic layer.
Fig. 5, Fig. 6 are cathode plasma electrolytic deposition ZrO
2-Y
2o
3the SEM shape appearance figure in composite ceramic layer surface topography and cross section, Fig. 7 is cathode plasma electrolytic deposition ZrO
2-Y
2o
3the EDS analytical results of composite ceramics layer cross section.As seen from the figure, surface plasma discharge differential of the arc comparatively small amt, is made up of cellular structure, and the EDS analytical results in the cross section in Fig. 7 is known, and ceramic layer is made up of Zr, Y, O, and is evenly distributed, and known ceramic phase is mainly ZrO
2and Y
2o
3.
Specific embodiment 4
Roughly the same with specific embodiment 1, difference is only: the solution in second step is the Titanium Nitrate aqueous solution of 20g/L.
Specific embodiment 5
Roughly the same with specific embodiment 2, difference is only: the solution in second step is the nickel nitrate aqueous solution of 30g/L.
Specific embodiment 6
Roughly the same with specific embodiment 1, difference is only: the solution in second step is the calcium nitrate aqueous solution of 40g/L.
Specific embodiment 7
Roughly the same with specific embodiment 1, difference is only: the solution in second step is the calcium nitrate aqueous solution of 40g/L.
Specific embodiment 8
Roughly the same with specific embodiment 1, difference is only: the solution in second step is the copper nitrate aqueous solution of 10g/L.
Specific embodiment 9
Roughly the same with specific embodiment 1, difference is only: the solution in second step is the chromium nitrate aqueous solution of 40g/L.
Specific embodiment 10
Roughly the same with specific embodiment 1, difference is only: the solution in second step is the chromium nitrate aqueous solution of 40g/L.
Specific embodiment 11
Roughly the same with specific embodiment 1, difference is only: the solution in second step is the iron nitrate aqueous solution of 40g/L.
Specific embodiment 12
Roughly the same with specific embodiment 1, difference is only: the solution in second step is the cerous nitrate aqueous solution of 30g/L.
Specific embodiment 13
Roughly the same with specific embodiment 3, difference is only: the solution in second step is the cerous nitrate of 5g/L and the zirconium nitrate aqueous solution of 5g/L.
Specific embodiment 14
Roughly the same with specific embodiment 3, difference is only: the solution in second step is the nickel nitrate aqueous solution of the aluminum nitrate of 5g/L, the magnesium nitrate of 5g/L and 5g/L.
Specific embodiment 15
Roughly the same with specific embodiment 3, difference is only: the solution in second step is the mixed aqueous solution of the cerous nitrate of the zirconium nitrate of 5g/L, the aluminum nitrate of 5g/L, the magnesium nitrate of 5g/L, the Titanium Nitrate of 5g/L, the Yttrium trinitrate of 5g/L, the nickelous nitrate of 5g/L, the nitrocalcite of 5g/L, the cupric nitrate of 5g/L, the chromium nitrate of 5g/L, the iron nitrate of 5g/L and 5g/L.
Specific embodiment 16
Roughly the same with specific embodiment 1, difference is only:
(1) adopt rare-earth salts chemical transformation at the prefabricated insulation barrier in aluminum alloy sample surface in a first step, concrete operations are as follows:
First according to cerous nitrate or Cerium II Chloride 45g/L, hydrogen peroxide 1ml/L adds deionized water to 1L, regulates PH to 4 obtain solution; Again above-mentioned rare earths salt is warming up to 80 DEG C, aluminum alloy sample is put into rare earths salt and reacts 30min.
(2) aqueous solution in second step is the zirconium nitrate of 8g/L and the yttrium nitrate aqueous solution of 1g/L.
Fig. 8 is the SEM pattern on the surface of insulating barrier films prepared by rare-earth salts chemical transformation, and Fig. 9 is the cathode plasma electrolytic deposition ZrO adopting the prefabricated blocking layer of rare-earth salts chemical transformation
2-Y
2o
3the SEM shape appearance figure of composite ceramics layer cross section.Rare-earth salts chemical transformation not only can provide the high resistance needed for cathode plasma electric discharge, can improve again the bonding strength of cathode plasma electrolytic deposition.
Specific embodiment 17
Roughly the same with specific embodiment 2, difference is only: adopt rare-earth salts chemical transformation at the prefabricated insulation barrier of magnesium alloy sample surfaces in a first step, concrete operations are as follows:
First according to Cerium II Chloride 50g/L, hydrogen peroxide 10ml/L adds deionized water to 1L, regulates PH to 6 obtained aqueous solution; Again above-mentioned rare earths salt is warming up to 90 DEG C, magnesium alloy sample is put into rare earths salt and reacts 20min.
Specific embodiment 18
Roughly the same with specific embodiment 1, difference is only: adopt rare-earth salts chemical transformation at the prefabricated insulation barrier in aluminum alloy sample surface in a first step, concrete operations are as follows:
First according to Cerium II Chloride 1g/L, hydrogen peroxide 0.1ml/L adds deionized water to 1L, regulates PH to 5 obtained aqueous solution; Again above-mentioned rare earths salt is warming up to 50 DEG C, aluminum alloy sample is put into described rare earths salt and react 60min.
By reference to the accompanying drawings embodiments of the present invention are elaborated above.But the present invention is not limited to above-mentioned embodiment, in the ken that art those of ordinary skill possesses, make a variety of changes under can also or else departing from the prerequisite of present inventive concept.
Claims (10)
1. a preparation method for oxide ceramic layer, is characterized in that, comprises the steps:
(1) by plasma electrolytic oxidation method or rare-earth salts chemical transformation at the prefabricated insulation barrier in alloy sample surface;
(2) configuration concentration is 5 ~ 50g/L nitrate aqueous solution;
(3) alloy sample described in step (1) is placed in solution described in step (2), described alloy sample is placed in negative electrode, anode is stainless steel or Graphite Electrodes, high energy pulse voltage is applied to described alloy sample, at described alloy surface deposition 0.5 ~ 3h, then prepare ceramic layer on described alloy sample surface.
2. the preparation method of a kind of oxide ceramic layer as claimed in claim 1, is characterized in that, described in step (1), alloy sample is before prefabricated insulation barrier, also needs pre-treatment, comprises the following steps:
(11) by described alloy sample acetone or alcohol washes;
(12) described for step (11) alloy sample sand paper is polished;
(13) by described for step (12) alloy sample washed with de-ionized water.
3. the preparation method of a kind of oxide ceramic layer as claimed in claim 1, is characterized in that, after described in step (3), ceramic layer is prepared on alloy sample surface, also needs to rinse with deionized water.
4. the preparation method of a kind of oxide ceramic layer as claimed in claim 1, is characterized in that, the method for the prefabricated insulation barrier of using plasma electrolytic oxidation in step (1), comprises the following steps:
(11) according to silicate 1 ~ 30g/L, phosphoric acid salt 1 ~ 20g/L, pH adjusting agent 1 ~ 5g/L prepare electrolytic solution, and solvent is deionized water;
(12) electrolytic solution described in step (11) is imported as in the stainless steel tank of negative electrode, described alloy sample, as anode, adopts the direct current pulse power source way of output to carry out the prefabricated insulation barrier of plasma electrolytic oxidation process to described alloy sample.
5. the preparation method of a kind of oxide ceramic layer as claimed in claim 4, is characterized in that, described silicate is water glass or potassium silicate; Described phosphoric acid salt is sodium phosphate or potassiumphosphate, and described PH conditioning agent is potassium hydroxide or sodium hydroxide.
6. the preparation method of a kind of oxide ceramic layer as claimed in claim 4, is characterized in that, the condition of carrying out plasma electrolytic oxidation process in described step (12) is: electric current 3 ~ 10A/dm
2, frequency 100 ~ 300Hz, dutycycle 30 ~ 50%, oxidization time is 3 ~ 10min.
7. the preparation method of a kind of oxide ceramic layer as claimed in claim 1, is characterized in that, adopts the method for the prefabricated insulation barrier of the chemical transformation of rare-earth salts, comprise the steps: described in step (1)
(11) according to cerous nitrate or Cerium II Chloride 1 ~ 50g/L, hydrogen peroxide 0.1 ~ 10ml/L adds deionized water to 1L, regulates PH to 4 ~ 6;
(12) rare earths salt described in step (11) is warming up to 50 ~ 90 DEG C, described alloy sample is put into described rare earths salt reaction 20 ~ 60min.
8. the preparation method of a kind of oxide ceramic layer as claimed in claim 1, it is characterized in that, nitrate described in step (2) is one or more in zirconium nitrate, aluminum nitrate, magnesium nitrate, Titanium Nitrate, Yttrium trinitrate, nickelous nitrate, nitrocalcite, cupric nitrate, chromium nitrate, iron nitrate or cerous nitrate.
9. the preparation method of a kind of oxide ceramic layer as claimed in claim 1, is characterized in that, the condition of carrying out high energy pulse in step (3) is for being pulsed current 3 ~ 30A/dm
2, pulsed voltage 300 ~ 1000V, frequency 100 ~ 1500Hz, dutycycle 5 ~ 50%.
10. the preparation method of a kind of oxide ceramic layer as claimed in claim 1, is characterized in that, described alloy refers to the one in magnesium alloy or aluminium alloy or magnalium.
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| CN106757249A (en) * | 2016-12-15 | 2017-05-31 | 河海大学常州校区 | A kind of cathode surface nanosecond pulsed electric field prepares the solution and preparation method of nano thin-film |
| CN107557836A (en) * | 2017-09-07 | 2018-01-09 | 西北工业大学 | TiAl alloy surface cathode micro arc plasma body electrolytic deposition prepares CeO2‑Al2O3The method of composite ceramic layer |
| CN111676499A (en) * | 2020-07-30 | 2020-09-18 | 华南理工大学 | Hydrogen-resistant coating based on cathode plasma electrolytic deposition and preparation method thereof |
| CN112538647A (en) * | 2020-10-29 | 2021-03-23 | 西安交通大学 | Method for preparing aluminum oxide-based ceramic coating by electrolyzing liquid phase plasma on surface of stainless steel |
| CN114032547A (en) * | 2021-11-10 | 2022-02-11 | 西北工业大学 | Alloy surface composite coating and preparation method thereof |
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